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CN1198688C - 成形催化剂 - Google Patents

成形催化剂 Download PDF

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CN1198688C
CN1198688C CN01112367.2A CN01112367A CN1198688C CN 1198688 C CN1198688 C CN 1198688C CN 01112367 A CN01112367 A CN 01112367A CN 1198688 C CN1198688 C CN 1198688C
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C·瓦尔斯多尔夫
O·霍夫斯塔德特
R·菲尔德
R·梅斯纳
K·哈斯
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Abstract

用于多相催化反应的成形催化剂，该催化剂的形状为端面相对于外缘和中心孔边缘都是圆形的空心圆柱体或环形片，即没有直角边缘。

Description

成形催化剂
                        技术领域
本发明涉及用于多相催化反应的新型成形催化剂，该催化剂的形状为端面相对于外缘和中心孔边缘都是圆形的空心圆柱体或环形片，以使它们没有直角边缘。
                        背景技术
EP-A-184790公开了用于多相催化反应的、形状为空心圆柱体的成形催化剂，在该圆柱体的外缘具有弯曲的端面。
WO-A-99/48606公开了形状为环形片的催化剂，该环形片的尺寸为5mm×5mm×2mm(高×直径×中心孔直径)。
但是，这些催化剂有些地方不能令人满意。尤其是，这些催化剂床层上的压降还不是最佳的。
本发明的目的是提供用于多相催化反应的、具有改良特性的、尤其是减少压降的成形催化剂。
                        发明内容
我们业已发现，这个目的是由用于多相催化反应的、形状为端面相对于外缘和中心孔边缘都是圆形的空心圆柱体或环形片的、新型改良催化剂(图1)实现的。
本发明提供一种用于多相催化反应、形状为空心圆柱体或环形片的成形催化剂，其中的作为外边缘的外壁截面(a)和作为中心孔边缘的内壁截面(b)是平的并且相互平行，而且其端面(c)相对于外边缘(a)和中心孔边缘(b)都是圆形的，以使得沿着中心孔观察，该催化剂体朝向该外边缘(a)和中心孔边缘(b)渐缩，空心圆柱体或环形片的外径是3-20mm，内径是外径的0.1-0.7倍，长度或高度是外径的0.2-2倍，并且端面曲率半径(R)是外径的0.01-0.5倍。
                        附图说明
图1所示为本发明成形催化剂的一种可能的剖面图。
图2所示为本发明实施例E1的成形催化剂的剖面图。
图3所示为对比例C3的成形催化剂的剖面图。
                        具体实施方式
本发明的催化剂是通过本身已知的方法制备的，例如，通过从其盐溶液中沉淀出各组分的氧化物、水合氧化物、氢氧化物或其它微溶化合物；或通过氧化的和/或盐类原材料的充分混合，该原材料可溶解和/或悬浮于水或有机溶剂中，随后干燥，并且如果适当的话，热分解这些盐类，磨成适当的可成片的颗粒尺寸，用适当的压片机成形为本发明的形状，并且如果适当的话，随后在氧化、还原或惰性环境中在升高的温度下进行热处理。在成形过程中的任意时刻可将成形助剂、增强材料添加到催化剂组合物中，所述成形助剂诸如石墨、碳黑、硬脂酸、淀粉、聚丙烯酸、矿物油、植物油、甲基纤维素等，所述增强材料诸如无机纤维例如玻璃纤维等，或无机粉末例如金属粉末、金属絮状物，惰性载体材料例如SiO2，金属硅酸盐类和硅酸铝、氧化铝、氢氧化铝、水合氧化铝、MgO、TiO2、ZrO2、Nb2O3、浮石、金刚砂和/或硅酸镁。
用于多相催化反应的本发明的成形催化剂，是形状为空心圆柱体或环形片的催化活性材料，或优选包括被加工成空心圆柱体或环形片的、其上涂布了催化活性组合物的惰性载体材料，这里空心圆柱体或环形片的外径是3-20mm，优选为3-10mm，特别优选为3-7mm，尤其是3.5-6.5mm，内径是外径的0.1-0.7倍，长度是外径的0.2-2倍，优选为0.3-1.8倍，特别优选为0.4-1.6倍，和端面曲率半径是外径的0.01-0.5倍，优选为0.05-0.4倍，特别优选为0.1-0.2倍。
这种新的催化剂形状，就具有载体的催化剂的情况而言也是有利的，这种催化剂是通过用呈氧化的或盐形式的组分的溶液或悬浮液进行浸渍、汽相沉积或喷涂来将活性组分涂敷到预成形的惰性载体上而制备的。
对催化剂的化学成分没有限制。
本发明的成形催化剂适用于多相催化反应，其中它们例如作为固定床用于气相或液相反应、尤其是强放热气相反应诸如由乙烯经氧氯化制备1，2-二氯乙烷。
本发明的成形催化剂，优选用于氧氯化，尤其是由乙烯制备1，2-二氯乙烷的氧氯化。适用于氧氯化的催化剂组合物，是基于优选含有高表面氧化铝诸如γ-或δ-Al2O3的载体。BET表面积通常是在100-250m2/g的范围内，优选在150-220m2/g的范围内。优选地，在第一步骤中，通过压片将该载体加工成所需的催化剂几何形状，并在随后的步骤中，将活性组分涂到该形状的载体上。在用于载体压片的原材料中，高表面氧化铝可完全地或部分地被其它化合物、诸如可通过焙烧转化成高表面氧化铝的假勃姆石替换。另外，还可将压片助剂诸如石墨或硬脂酸镁加到待压片的原材料中。优选使用如WO-A-99/48606所述的压片混合物。
根据本发明，将原料压片制成空心圆柱体或环形片。空心圆柱体或环通常具有3-7mm的算术平均高度，优选为4.8-5.2mm，特别优选为4.9-5.1mm，算术平均直径为3-7mm，优选为4.8-5.2mm，特别优选为4.9-5.1mm，中心孔的算术平均直径为2-3.5mm，优选为2.3-2.7mm，特别优选为2.4-2.6mm。
在压片后，通常将该催化剂载体焙烧。焙烧通常在500-800℃，优选在700-750℃下进行。焙烧通常在氧化环境中，一般在空气中进行。
所述的压片方法和原材料的选择，通常产生出既具有好的机械稳定性又具有有利于氧氯化的孔容的催化剂载体。这些根据本发明获得的、用于氧氯化的催化剂载体，通常孔容为0.1-0.9cm3/g，优选为0.3-0.7cm3/g，特别优选为0.4-0.6cm3/g，和侧向压缩强度至少为20N，优选为22-80N，特别优选为25-60N，尤其是27-55N。
随后，可用CuCl2和，如果需要的话，其它化合物诸如KCl，其它碱金属、碱土金属或稀土金属的盐类的溶液，浸渍用这种方法获得的载体。如果需要的话，还可将盐酸加到该溶液中。
浸渍溶液的体积有利的是选择为，使它对应于载体孔容的10-200％，优选为30-150％，特别优选为90-110％。
在浸渍之后，通常将该成形催化剂坯体在80-300℃，优选100-200℃下干燥。
选择浸渍溶液的浓度和体积，以使该载于载体上的催化剂通常含有Cu含量为1-15重量％，优选为2-10重量％，和K含量为0.1-8重量％，优选为0.3-3重量％。该催化剂组合物的活性分布类型按需要设置：通过选择催化剂中的金属浓度、和如果需要的话，用惰性材料诸如Al2O3进行稀释。可由这种方法得到的载于载体上的催化剂，适用于由氧氯化制备1，2-二氯乙烷。该催化剂将低的压降与良好的机械强度相结合。
本发明的催化剂载体的总孔容(Hg孔度计)至少为0.35ml/g，优选至少为0.4ml/g，大孔占全部孔容的比例至少为10％，优选为15-50％，特别优选为20-40％。
这种新的成形催化剂，优选适用于乙烯的氧氯化，并且通常还适用于其它多相催化反应，例如用于制备丙烯酸、邻苯二甲酸酐和马来酐，或用于烷烃脱氢制备烯烃，例如由丙烷制备丙烯。为这种和其它反应设计的、根据本发明成形催化剂的制备，除根据本发明加工成形外，可类似于适用于这种反应的其它催化剂的制备来进行。这些催化剂可以是载于载体上的催化剂或者是无载体的催化剂。
实施例E1
将如WO 99/48606中所述的干燥混合物压片，制成尺寸为5mm×5mm×2.5mm(高×直径×中心孔直径)、并且如图2所示端面相对于外缘和中心孔边缘是圆形的、侧向压缩强度为20N的环形片，随后，将这些环形片在700℃焙烧2个小时。载体的物理数据如表1所示。
实施例E1*
将载体E1用氯化铜和氯化钾的溶液浸渍成铜含量为5.8％和钾含量为2.6％。为此，将相当于吸水率的体积的氯化铜和氯化钾的溶液浇到载体上，并将该浸渍的催化剂在120℃干燥。
对比例C1
按如WO 99/48606中所述，将与E1中同样的干燥混合物压片，制成尺寸为5mm×5mm×2mm(高×直径×中心孔直径)的环形片，并将这些环形片焙烧。
实施例C1*
将载体C1用氯化铜和氯化钾的溶液浸渍成铜含量为5.8％和钾含量为2.6％。为此，将相当于吸水率的体积的氯化铜和氯化钾的溶液浇到载体上，并将该浸渍的催化剂在120℃干燥。
对比例C2
将与E1中同样的干燥混合物压片，制成尺寸为5mm×5mm×2.5mm(高×直径×中心孔直径)和侧向压缩强度为20N的环形片，随后，将这些环形片在700℃焙烧2个小时。
对比例C3
将与E1中同样的干燥混合物压片，制成尺寸为5mm×5mm×2.5mm(高×直径×中心孔直径)、和具有如图3所示圆形端面的、且侧向压缩强度为20N的环形片，并将这些环形片焙烧。
压降测定
在位于直径为2.5cm的玻璃管中的长度为1米的床层上进行压降测定。用于强放热多相催化气相反应诸如由乙烯制备二氯乙烷的氧氯化的工业壳一管式反应器，典型的是直径约为2.5cm的反应管。为得到尽可能均匀的小块，以及由此易于再现的数值，在每种情况下都将载体经漏斗缓慢加入，以使这些载体连续地和实际上分别落到彼此的顶部。
性能测试
将来自实施例E1*和对比例C1*的催化剂，在循环反应器中、以1molHCl/90ml催化剂的生产量、并使用由氯化氢、乙烯和空气组成的化学计量进料进行测试。表3显示出乙烯转化率和燃烧选择性。
表1载体的物理数据
侧向压缩强度(N) 孔容(ml/g) BET表面积(m2/g) 吸水率(ml/g)
实施例E1  25  0.42  160  0.48
对比例C1  31  0.43  197  0.52
对比例C2  24  0.41  177  0.50
对比例C3  25  0.41  170  0.51
表2：直径为2.5cm的管中、1m床层上的相对压降
N2流率(标准m3/h)2bar 对比例C1床层重量：303.4gΔP(mmH2O) 对比例C3床层重量：280.6gΔP(mmH2O) 对比例C2床层重量：280.9gΔP(mmH2O) 实施例E1床层重量：284gΔP(mmH2O)  相对压降
1.138  122  116  112  104  1∶0.95∶0.92∶0.85
1.834  366  346  335  308  1∶0.95∶0.92∶0.85
2.711  736  705  679  625  1∶0.95∶0.92∶0.85
表3本发明的催化剂和对比催化剂的性能
温度(℃) 乙烯转化率(％) 燃烧产生CO+CO2的选择率(％) 对氯化副产物的选择率(％)
实施例E1* 240  70  0.46  1.39
对比例C1* 240  72.7  0.69  1.49
实施例E1* 270  79.6  2.65  4.72
对比例C1* 270  78.7  3.1  4.83
本发明成形催化剂的压降，比WO-A-99/48606所述的、形状为5mm×5mm×2mm环形片(对比例C1)催化剂压降低约15％。与对比例C2和C3的载体几何形状进行对比，来自实施例E1的载体的新形状也显示出显著降低了的压降，即分别降低11％和降低8％。载体C2是在压降方面对载体C1进行改进的，根据WO-A-99/48606中的说明，这种改进对该技术领域技术人员来说是显而易见的。C3是根据EP-A-184790的教导，对载体C2作的改进。由于对比的所有载体实际上具有相同的外部尺寸，并在相同管径的典型工业反应管中进行研究，这些结果非常清楚地显示出具有本发明的形状的催化剂改进的压降。
通过催化剂C1*和E1*的对比，表现出本发明载体几何形状对于氧氯化中相应的催化剂的性能的优点。具有本发明形状的催化剂(E1*)，与具有已知形状的催化剂(C1)对比，在大约相同的转化率下显示出明显改进的选择性。

Claims (12)

1.一种用于多相催化反应的成形催化剂，其形状为空心圆柱体或环形片，其中的作为外边缘(a)的外壁截面和作为中心孔边缘(b)的内壁截面是平的并且相互平行，而且其端面(c)相对于外边缘(a)和中心孔边缘(b)都是圆形的，以使得沿着中心孔观察，该催化剂体朝向该外边缘(a)和中心孔边缘(b)渐缩，空心圆柱体或环形片的外径是3-20mm，内径是外径的0.1-0.7倍，长度或高度是外径的0.2-2倍，并且端面曲率半径(R)是外径的0.01-0.5倍。
2.如权利要求1的用于多相催化反应的成形催化剂，该催化剂是通过将BET表面积为100-250m2/g的成形γ-Al2O3载体，用CuCl2和以下存在或不存在的物质浸渍制得的：KCl、除KCl之外的其它碱金属、碱土金属或稀土金属的盐。
3.如权利要求2的用于多相催化反应的成形催化剂，其中被浸渍的盐是以其氯化物的形式存在的。
4.一种如权利要求1的用于多相催化反应的成形催化剂的制备方法，该方法包括，
将含有BET表面积为100-250m2/g的氧化铝材料压片，以得到成形的载体；
在500-800℃下焙烧所述成形载体，以得到Hg孔度计测得的总孔容至少为0.35ml/g的催化剂载体；
用CuCl2和以下存在或不存在的物质的溶液浸渍所述载体：KCl、除KCl以外的其它碱金属、碱土金属或稀土金属的盐类，以得到成形催化剂坯体，其中浸渍溶液的体积为载体总孔容的10-200％；和
在80-300℃下干燥该成形催化剂坯体。
5.如权利要求1的成形催化剂在放热气相反应中的应用。
6.如权利要求2或3的成形催化剂在放热气相反应中的应用。
7.如权利要求1的成形催化剂在氧氯化反应中的应用。
8.如权利要求2或3的成形催化剂在氧氯化反应中的应用。
9.如权利要求1的成形催化剂在由乙烯的氧氯化制备1，2-二氯乙烷中的应用。
10.如权利要求2或3的成形催化剂在由乙烯的氧氯化制备1，2-二氯乙烷中的应用。
11.一种制备1，2-二氯乙烷的方法，其中使用如权利要求1的成形催化剂。
12.一种制备1，2-二氯乙烷的方法，其中使用如权利要求2或3的成形催化剂。
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